Templated monolayer polymerization and replication

Abstract

A self-replicating monolayer system employing polymerization of monomers or nanoparticle ensembles on a defined template provides a method for synthesis of two-dimensional single molecule polymers. Systems of self-replicating monolayers are used as templates for growth of inorganic colloids. A preferred embodiment employs SAM-based replication, wherein an initial monolayer is patterned and used as a template for self-assembly of a second monolayer by molecular recognition. The second monolayer is polymerized in place and the monolayers are separated to form a replicate. Both may then function as templates for monolayer assemblies. A generic self-replicating monomer unit comprises a polymerizable moiety attached by methylene repeats to a recognition element and an ending unit that will not interfere with the chosen recognition chemistry. The recognition element is self-complementary, unless a set of two replicating monomers with compatible cross-linking chemistry is employed. In a two-component replication system utilizing two different kinds of recognition chemistries, the initial template undergoes replication cycles, while maintaining two-dimensional segregation of the two types of monomers. During subsequent replications, the component domains experience little or no mixing, allowing the two-component, patterned assembly to be exponentially replicated. After replication, selective mineralization and/or electroless plating may produce a two-dimensional inorganic sheet having patterned domains within it.

1. A method for replicating a monolayer comprising the steps of:
 forming a first set of monomers into a first patterned monolayer having a desired pattern; 
 attaching a second set of monomers to the first patterned monolayer, forming a second patterned monolayer attached to the first patterned monolayer; 
 polymerizing the second patterned monolayer, forming a replicated monolayer attached to the first patterned monolayer; and 
 disassociating the replicated monolayer from the first patterned monolayer. 
 
     
     
       2. The method of  claim 1 , further comprising the step of polymerizing the first patterned monolayer. 
     
     
       3. The method of  claim 2  wherein the step of polymerizing the first patterned monolayer employs a topochemical polymerization. 
     
     
       4. The method of  claim 1 , wherein the monomers are nucleotides or oligonucleotides. 
     
     
       5. The method of  claim 1 , wherein the monomers are amino acids. 
     
     
       6. The method of  claim 1 , wherein the monomers are nanoparticle ensembles. 
     
     
       7. The method of  claim 1 , wherein the monomers contain at least two reactive functional groups. 
     
     
       8. The method of  claim 1 , wherein the monomers contain a terminus bearing one or more molecular recognition elements. 
     
     
       9. The method of  claim 1 , further including the step of creating at least one additional replicated monolayer by utilizing the disassociated replicated monolayer in place of the first patterned monolayer in the steps of attaching, polymerizing, and disassociating. 
     
     
       10. The method of  claim 1 , wherein the monomers are selected from the group consisting of Hentriaconta-11,13,20,22-tetraynoic acid, Hentriaconta-11,13,20,22-tetraynoic acid amide, Triaconta-10,12,19,21-tetraynoic acid amide, and Triaconta-10,12,19,21-tetraynoic acid. 
     
     
       11. The method of  claim 1 , further including the step of selective mineralization of the disassociated replicated monolayer. 
     
     
       12. The method of  claim 1 , further including the step of electroless plating of the disassociated replicated monolayer. 
     
     
       13. The method of  claim 1 , further including the steps of nanoparticle adhesion to, and sintering of, the disassociated replicated monolayer. 
     
     
       14. The method of  claim 1 , further including the step of growing an inorganic structure upon the disassociated replicated monolayer. 
     
     
       15. The method of  claim 1 , wherein the step of polymerizing the second patterned monolayer employs a topochemical polymerization.